U.S. patent application number 15/086185 was filed with the patent office on 2016-10-06 for chain transfer agent for addition mass polymerization of polycycloolefinic monomers.
The applicant listed for this patent is PROMERUS, LLC. Invention is credited to HENDRA NG, KEITARO SETO, WEI ZHANG.
Application Number | 20160289353 15/086185 |
Document ID | / |
Family ID | 55863186 |
Filed Date | 2016-10-06 |
United States Patent
Application |
20160289353 |
Kind Code |
A1 |
NG; HENDRA ; et al. |
October 6, 2016 |
CHAIN TRANSFER AGENT FOR ADDITION MASS POLYMERIZATION OF
POLYCYCLOOLEFINIC MONOMERS
Abstract
The present invention relates to use of certain chain transfer
agents to control molecular weight of addition mass polymerization
of certain polycycloolefinic monomers. More specifically, the
present invention relates to use of a series of substituted
bicycloalkenes as chain transfer agents in the addition mass
polymerization of a series of functionalized norbornene-type
monomers. This invention also relates to compositions containing
bicycloalkenes as chain transfer agents in forming "in mold"
polycycloolefinic polymers by addition mass polymerization.
Inventors: |
NG; HENDRA; (BRECKSVILLE,
OH) ; SETO; KEITARO; (BRECKSVILLE, OH) ;
ZHANG; WEI; (BRECKSVILLE, US) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PROMERUS, LLC |
Brecksville |
OH |
US |
|
|
Family ID: |
55863186 |
Appl. No.: |
15/086185 |
Filed: |
March 31, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62140514 |
Mar 31, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 132/08 20130101;
C08F 2/38 20130101; C08F 2/02 20130101 |
International
Class: |
C08F 132/08 20060101
C08F132/08 |
Claims
1. A reaction composition comprising: a compound of formula (I):
##STR00018## wherein a is an integer from 0 to 4; b is an integer
from 0 to 2a+4; each R is hydrogen, halogen, methyl, ethyl, linear
or branched (C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy, linear or branched
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy; one or more polycyclic olefin
monomers; and an organo-transition metal compound.
2. The composition of claim 1, wherein said one or more polycyclic
olefin monomer is of formula (II): ##STR00019## wherein: c is an
integer 0, 1 or 2; R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the
same or different and each independently of one another is selected
from hydrogen, linear or branched (C.sub.1-C.sub.16)alkyl,
hydroxy(C.sub.1-C.sub.16)alkyl, perfluoro(C.sub.1-C.sub.12)alkyl,
(C.sub.3-C.sub.12)cycloalkyl, (C.sub.6-C.sub.12)bicycloalkyl,
(C.sub.7-C.sub.14)tricycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.3)alkyl,
perfluoro(C.sub.6-C.sub.10)aryl,
perfluoro(C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.3)alkyl,
di(C.sub.1-C.sub.2)alkylmaleimide(C.sub.3-C.sub.6)alkyl,
di(C.sub.1-C.sub.2)alkylmaleimide(C.sub.2-C.sub.6)alkoxy(C.sub.1-C.sub.2)-
alkyl, hydroxy, (C.sub.1-C.sub.12)alkoxy,
(C.sub.3-C.sub.12)cycloalkoxy, (C.sub.6-C.sub.12)bicycloalkoxy,
(C.sub.7-C.sub.14)tricycloalkoxy,
(C.sub.6-C.sub.10)aryloxy(C.sub.1-C.sub.3)alkyl,
(C.sub.5-C.sub.10)heteroaryloxy(C.sub.1-C.sub.3)alkyl,
(C.sub.6-C.sub.10)aryloxy, (C.sub.5-C.sub.10)heteroaryloxy,
(C.sub.1-C.sub.6)acyloxy, where each of the aforementioned
substituents are optionally substituted with a group selected from
halogen or hydroxy.
3. The composition of claim 1, wherein said compound of formula (I)
is selected from the group consisting of: bicyclo[3.2.0]hept-6-ene;
2-methylbicyclo[3.2.0]hept-6-ene;
2,4-dimethylbicyclo[3.2.0]hept-6-ene;
2,4,6-trimethylbicyclo[3.2.0]hept-6-ene; bicyclo[4.2.0]oct-7-ene;
2-methylbicyclo[4.2.0]oct-7-ene; 3-methylbicyclo[4.2.0]oct-7-ene;
2,3-dimethylbicyclo[4.2.0]oct-7-ene;
2,3,5-trimethylbicyclo[4.2.0]oct-7-ene;
2,3,4,5-tetramethylbicyclo[4.2.0]oct-7-ene;
bicyclo[5.2.0]non-8-ene; 2-methylbicyclo[5.2.0]non-8-ene;
2,5-dimethylbicyclo[5.2.0]non-8-ene; bicyclo[6.2.0]dec-9-ene; and
2-methylbicyclo[6.2.0]dec-9-ene.
4. The composition of claim 1, wherein said organo-transition metal
compound is selected from the group consisting of: ##STR00020##
wherein Py is pyridine.
5. The composition of claim 1, wherein said organo-transition metal
compound is selected from the group consisting of: ##STR00021##
6. The composition of claim 1, wherein said organo-transition metal
compound is selected from the group consisting of:
trans-[Pd(NCMe)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub.6F.sub.5).sub.4,
trans-[Pd(NCC(CH.sub.3).sub.3)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub.6F.s-
ub.5).sub.4,
trans-[Pd(OC(C.sub.6H.sub.5).sub.2)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub-
.6F.sub.5).sub.4,
trans-[Pd(HOCH(CH.sub.3).sub.2)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub.6F.-
sub.5).sub.4,
trans-[Pd(NCMe)(OAc)(P(cyclohexyl).sub.3).sub.2]B(C.sub.6F.sub.5).sub.4,
Pd(OAc).sub.2(P(cyclohexyl).sub.3).sub.2,
Pd(OAc).sub.2(P(i-propyl).sub.3).sub.2,
Pd(OAc).sub.2(P(i-propyl).sub.2(phenyl)).sub.2,
trans-[Pd(NCMe)(OAc)(P(cyclohexyl).sub.2(t-butyl)).sub.2]B(C.sub.6F.sub.5-
).sub.4, where OAc is OCOCH.sub.3.
7. The composition of claim 1, wherein said organo-transition metal
compound is selected from the group consisting of:
nickel(2,4,6-trifluoromethylphenyl).sub.2;
nickel(.eta..sup.6-toluene)(pentafluorophenyl).sub.2; nickel
(tetrahydrofuran).sub.2(pentafluorophenyl).sub.2;
[(allyl)Ni(1,4-cyclooctadiene)]PF.sub.6,
[(crotyl)Ni(1,4-cyclooctadiene)]PF.sub.6; and
[(allyl)Ni(1,4-cyclooctadiene)]SbF.sub.6.
8. The composition of claim 1 further comprising a compound of the
formula (V): M.sup..sym.Z.sup..crclbar. (V); wherein M.sup..sym. is
a cation selected from lithium, sodium, potassium, cesium, barium,
ammonium and linear or branched tetra(C.sub.1-C.sub.4)alkyl
ammonium; Z.sup..crclbar. is a weakly coordinating anion selected
from B(C.sub.6F.sub.5).sub.4.sup..crclbar.,
B[C.sub.6H.sub.3(CF.sub.3).sub.2].sub.4.sup..crclbar.,
B(C.sub.6H.sub.5).sub.4.sup..crclbar.,
[Al(OC(CF.sub.3).sub.2C.sub.6F.sub.5).sub.4].sup..crclbar.,
BF.sub.4.sup..crclbar., PF.sub.6.sup..crclbar.,
AsF.sub.6.sup..crclbar., SbF.sub.6.sup..crclbar.,
(CF.sub.3SO.sub.2)N.sup..crclbar. and
CF.sub.3SO.sub.3.sup..crclbar..
9. The composition of claim 8, wherein said compound of the formula
(V) is selected from the group consisting of: lithium
tetrafluoroborate; lithium triflate; lithium
tetrakis(pentafluorophenyl)borate; lithium tetraphenylborate;
lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; lithium
tetrakis(2-fluorophenyl)borate; lithium
tetrakis(3-fluorophenyl)borate; lithium
tetrakis(4-fluorophenyl)borate; lithium
tetrakis(3,5-difluorophenyl)borate; lithium hexafluorophosphate;
lithium hexaphenylphosphate; lithium
hexakis(pentafluorophenyl)phosphate; lithium hexafluoroarsenate;
lithium hexaphenylarsenate; lithium
hexakis(pentafluorophenyl)arsenate; lithium
hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; lithium
hexafluoroantimonate; lithium hexaphenylantimonate; lithium
hexakis(pentafluorophenyl)antimonate; lithium
hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; lithium
tetrakis(pentafluorophenyl)aluminate; lithium
tris(nonafluorobiphenyl)fluoroaluminate; lithium
(octyloxy)tris(pentafluorophenyl)aluminate; lithium
tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; and lithium
methyltris(pentafluorophenyl)aluminate
10. The composition of claim 1, wherein said one or more monomer of
formula (II) is selected from the group consisting of:
bicyclo[2.2.1]hept-2-ene (NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-decylbicyclo[2.2.1]hept-2-ene (DecNB);
5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C.sub.4F.sub.9NB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).
11. The composition of claim 1, wherein said one or more monomers
of formula (II) are at least two distinct types of monomers of
formula (II).
12. The composition of claim 1, wherein at least one of said one or
more monomers of formula (II) is 5-decylbicyclo[2.2.1]hept-2-ene
(DecNB) or 5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB).
13. The composition of claim 1, wherein at least one of said one or
more monomers of formula (II) is
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB).
14. The composition of claim 1, wherein said compound of formula
(I) is present in an amount of at least one mole percent of the
total loading of the monomers of formula (II).
15. The composition of claim 1, wherein said compound of formula
(I) is present in an amount of from one to ten mole percent of the
total loading of the monomers of formula (II).
16. A method of mass polymerizing polycyclic olefin monomers
comprising: combining a compound of formula (I): ##STR00022##
wherein a is an integer from 0 to 4; b is an integer from 0 to
2a+4; each R is hydrogen, halogen, methyl, ethyl,
(C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy,
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy; with one or more polycyclic olefin
monomers; and an organo-transition metal compound to form a
mixture; and polymerizing the mixture to form a polymer.
17. The method of claim 16, wherein said compound of formula (I)
activates said organo-transition metal compound by forming a
metal-hydride containing moiety.
18. The method of claim 16, wherein said organo-transition metal
compound is a palladium compound.
19. The method of claim 16, which further comprises adding one or
more compounds of the formula (V): M.sup..sym.Z.sup..crclbar. (V);
wherein M.sup..sym. is a cation selected from lithium, sodium,
potassium, cesium, barium, ammonium and linear or branched
tetra(C.sub.1-C.sub.4)alkyl ammonium; Z.sup..crclbar. is a weakly
coordinating anion selected from
B(C.sub.6F.sub.5).sub.4.sup..crclbar.,
B[C.sub.6H.sub.3(CF.sub.3).sub.2].sub.4.sup..crclbar.,
B(C.sub.6H.sub.5).sub.4.sup..crclbar.,
[Al(OC(CF.sub.3).sub.2C.sub.6F.sub.5).sub.4].sup..crclbar.,
BF.sub.4.sup..crclbar., PF.sub.6.sup..crclbar.,
AsF.sub.6.sup..crclbar., SbF.sub.6.sup..crclbar.,
(CF.sub.3SO.sub.2)N.sup..crclbar. and
CF.sub.3SO.sub.3.sup..crclbar..
20. The method of claim 16, wherein said organo-transition compound
is selected from the group consisting of: ##STR00023## wherein Py
is pyridine.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/140,514, filed Mar. 31, 2015, which is
incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to use of certain chain
transfer agents to control molecular weight of addition mass
polymerization of certain polycycloolefinic monomers. More
specifically, the present invention relates to use of a series of
substituted bicycloalkenes as chain transfer agents in the addition
mass polymerization of a series of functionalized norbornene-type
monomers. This invention also relates to compositions containing
bicycloalkenes as chain transfer agents in forming "in mold"
polycycloolefinic polymers by addition mass polymerization.
[0004] 2. Description of the Art
[0005] Cyclic olefin polymers, such as polynorbornenes (PNBs), are
widely used in a variety of electronic, optoelectronic and other
applications, and therefore, methods of making such PNBs in an
industrial scale are of importance. It is well known in the
literature that various functionalized PNBs can be synthesized by
employing suitable starting norbornene monomers by addition
polymerization using a variety of transition metal catalysts and
procatalysts. See for example, U.S. Pat. No. 7,989,570, pertinent
portions of which are incorporated herein by reference.
[0006] It is also known in the literature that certain of the
aforementioned vinyl addition polymerization methods result in very
high molecular weight polymers, which may not always be desirable,
such as for example, high molecular weight polymers become less
soluble in commonly used solvents, and therefore, can't be used in
many applications involving any solvent based compositions.
Accordingly, it has been reported in the literature that certain
chain transfer agents can be used in the vinyl addition
polymerization methods in order to control the molecular weight.
See for example, U.S. Pat. No. 5,468,819, where it is disclosed use
of an olefinic chain transfer agent to control the molecular weight
of an addition polymer in solution. Similarly, U.S. Pat. No.
7,759,439 and U.S. Pat. No. 7,863,394 disclose respectively use of
formic acid and non-olefinic compound (such as silane, germane and
stannane) as chain transfer agent in solution phase addition
polymerization.
[0007] In some applications, such as, electronics applications, the
polymer formed from the addition solution polymerization must
undergo several process steps which involve removing the metal
catalyst and the solvent. This further may involve different
polymerization solvent and carrier solvent for the compositions
employed in the electronic applications. These additional steps
also create considerable amounts of solid and liquid waste which
needs to be disposed, which are environmentally not friendly and
also expensive.
[0008] Accordingly, there is a need to develop a method to mass
addition polymerization of polycycloolefinic monomers such that
controlled molecular weight polymers can be prepared without
adversely affecting the reactivity and final monomer conversion.
More importantly, such polymers are formed without the use of any
solvents, and should feature good thermal and mechanical
properties.
[0009] Accordingly, it is an object of this invention to provide a
series of bicycloalkenes having utility as chain transfer agents in
mass addition polymerization of a variety of cycloolefinic
monomers.
[0010] It is also an object of this invention to provide
compositions to form controlled molecular weight polymers by mass
addition polymerization techniques as disclosed herein.
[0011] Other objects and further scope of the applicability of the
present invention will become apparent from the detailed
description that follows.
SUMMARY OF THE INVENTION
[0012] Surprisingly, it has now been found that certain of the
non-polar organic molecules and more specifically a series of
substituted bicycloalkenes offer unique advantages as chain
transfer agents to mass polymerize a variety of cyclic olefin
monomers including but not limited to a variety of functionalized
norbornene monomers. Among some of the advantages offered by these
chain transfer agents (CTAs) include but are not limited to a)
reducing the amount of the initiator to form the final polymer
having very low levels of any residual metal initiator; b)
controlling polymerization activity of the organo-metallic
initiators employed; c) effective in reducing the molecular weight
of the resulting polycycloolefinic polymers; d) readily tailorable
to the required molecular weight of the polymer by controlling the
reaction kinetics thereby resulting in minimum adverse effects on
reaction kinetics and monomer conversion; e) low dielectric
polymers can be formed; among others. In some aspects, the chain
transfer agents as employed herein offers unique methods to form
polymers exhibiting excellent fire retardant properties. In other
aspects of this invention, the CTAs as employed herein provides
hitherto unobtainable melt processable polycycloolefinic polymers.
In further aspects of this invention, the CTAs of this invention
provides for telechelic oligomeric and/or polymeric materials with
end group functionalities having utility in various other
applications.
[0013] Accordingly, there is provided a reaction composition
comprising:
[0014] a compound of formula (I):
##STR00001##
[0015] wherein
[0016] a is an integer from 0 to 4;
[0017] b is an integer from 0 to 2a+4;
[0018] each R is hydrogen, halogen, methyl, ethyl, linear or
branched (C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy, linear or branched
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy;
[0019] one or more polycyclic olefin monomers; and
[0020] an organo-transition metal compound.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Embodiments in accordance with the present invention are
described below with reference to the following accompanying
figures and/or images. Where drawings are provided, it will be
drawings which are simplified portions of various embodiments of
this invention and are provided for illustrative purposes only.
[0022] FIG. 1 shows a thermogram from thermogravimetric analysis
(TGA) of a composition in accordance with one of the embodiments of
the invention.
[0023] FIG. 2 shows a thermogram from thermogravimetric analysis
(TGA) of a comparative composition.
DETAILED DESCRIPTION
[0024] The terms as used herein have the following meanings:
[0025] As used herein, the articles "a," "an," and "the" include
plural referents unless otherwise expressly and unequivocally
limited to one referent.
[0026] Since all numbers, values and/or expressions referring to
quantities of ingredients, reaction conditions, etc., used herein
and in the claims appended hereto, are subject to the various
uncertainties of measurement encountered in obtaining such values,
unless otherwise indicated, all are to be understood as modified in
all instances by the term "about."
[0027] Where a numerical range is disclosed herein such range is
continuous, inclusive of both the minimum and maximum values of the
range as well as every value between such minimum and maximum
values. Still further, where a range refers to integers, every
integer between the minimum and maximum values of such range is
included. In addition, where multiple ranges are provided to
describe a feature or characteristic, such ranges can be combined.
That is to say that, unless otherwise indicated, all ranges
disclosed herein are to be understood to encompass any and all
sub-ranges subsumed therein. For example, a stated range of from "1
to 10" should be considered to include any and all sub-ranges
between the minimum value of 1 and the maximum value of 10.
Exemplary sub-ranges of the range 1 to 10 include, but are not
limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc.
[0028] As used herein, the symbol "" denotes a position at which
the bonding takes place with another repeat unit or another atom or
molecule or group or moiety as appropriate with the structure of
the group as shown.
[0029] As used herein, "hydrocarbyl" refers to a radical of a group
that contains carbon and hydrogen atoms, non-limiting examples
being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The
term "halohydrocarbyl" refers to a hydrocarbyl group where at least
one hydrogen has been replaced by a halogen. The term perhalocarbyl
refers to a hydrocarbyl group where all hydrogens have been
replaced by a halogen.
[0030] As used herein, the expression "(C.sub.1-C.sub.6)alkyl"
includes methyl and ethyl groups, and straight-chained or branched
propyl, butyl, pentyl and hexyl groups. Particular alkyl groups are
methyl, ethyl, n-propyl, isopropyl and tert-butyl. Derived
expressions such as "(C.sub.1-C.sub.4)alkoxy",
"(C.sub.1-C.sub.4)thioalkyl"
"(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl",
"hydroxy(C.sub.1-C.sub.4)alkyl", "(C.sub.1-C.sub.4)alkylcarbonyl",
"(C.sub.1-C.sub.4)alkoxycarbonyl(C.sub.1-C.sub.4)alkyl",
"(C.sub.1-C.sub.4)alkoxycarbonyl", "amino(C.sub.1-C.sub.4)alkyl",
"(C.sub.1-C.sub.4)alkylamino",
"(C.sub.1-C.sub.4)alkylcarbamoyl(C.sub.1-C.sub.4)alkyl",
"(C.sub.1-C.sub.4)dialkylcarbamoyl(C.sub.1-C.sub.4)alkyl" "mono- or
di-(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl",
"amino(C.sub.1-C.sub.4)alkylcarbonyl"
"diphenyl(C.sub.1-C.sub.4)alkyl", "phenyl(C.sub.1-C.sub.4)alkyl",
"phenylcarboyl(C.sub.1-C.sub.4)alkyl" and
"phenoxy(C.sub.1-C.sub.4)alkyl" are to be construed
accordingly.
[0031] As used herein, the expression "cycloalkyl" includes all of
the known cyclic radicals. Representative examples of "cycloalkyl"
includes without any limitation cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
Derived expressions such as "cycloalkoxy", "cycloalkylalkyl",
"cycloalkylaryl", "cycloalkylcarbonyl" are to be construed
accordingly.
[0032] As used herein, the expression "(C.sub.2-C.sub.6)alkenyl"
includes ethenyl and straight-chained or branched propenyl,
butenyl, pentenyl and hexenyl groups. Similarly, the expression
"(C.sub.2-C.sub.6)alkynyl" includes ethynyl and propynyl, and
straight-chained or branched butynyl, pentynyl and hexynyl
groups.
[0033] As used herein the expression "(C.sub.1-C.sub.4)acyl" shall
have the same meaning as "(C.sub.1-C.sub.4)alkanoyl", which can
also be represented structurally as "R--CO--," where R is a
(C.sub.1-C.sub.3)alkyl as defined herein. Additionally,
"(C.sub.1-C.sub.3)alkylcarbonyl" shall mean same as
(C.sub.1-C.sub.4)acyl. Specifically, "(C.sub.1-C.sub.4)acyl" shall
mean formyl, acetyl or ethanoyl, propanoyl, n-butanoyl, etc.
Derived expressions such as "(C.sub.1-C.sub.4)acyloxy" and
"(C.sub.1-C.sub.4)acyloxyalkyl" are to be construed
accordingly.
[0034] As used herein, the expression
"(C.sub.1-C.sub.6)perfluoroalkyl" means that all of the hydrogen
atoms in said alkyl group are replaced with fluorine atoms.
Illustrative examples include trifluoromethyl and pentafluoroethyl,
and straight-chained or branched heptafluoropropyl,
nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl groups.
Derived expression, "(C.sub.1-C.sub.6)perfluoroalkoxy", is to be
construed accordingly.
[0035] As used herein, the expression "(C.sub.6-C.sub.10)aryl"
means substituted or unsubstituted phenyl or naphthyl. Specific
examples of substituted phenyl or naphthyl include o-, p-, m-tolyl,
1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc.
"Substituted phenyl" or "substituted naphthyl" also include any of
the possible substituents as further defined herein or one known in
the art. Derived expression, "(C.sub.6-C.sub.10)arylsulfonyl," is
to be construed accordingly.
[0036] As used herein, the expression
"(C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl" means that the
(C.sub.6-C.sub.10)aryl as defined herein is further attached to
(C.sub.1-C.sub.4)alkyl as defined herein. Representative examples
include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl,
2-naphthylmethyl and the like. It should be further noted that the
expressions "arylalkyl" and "aralkyl" mean the same are used
interchangeably. Accordingly, the expression
"(C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.4)alkyl" can also be
construed as "(C.sub.6-C.sub.14)aralkyl."
[0037] "Halogen" or "halo" means chloro, fluoro, bromo, and
iodo.
[0038] In a broad sense, the term "substituted" is contemplated to
include all permissible substituents of organic compounds. In a few
of the specific embodiments as disclosed herein, the term
"substituted" means substituted with one or more substituents
independently selected from the group consisting of C.sub.1-6
alkyl, C.sub.2-6alkenyl, C.sub.1-6 perfluoroalkyl, phenyl, hydroxy,
--CO.sub.2H, an ester, an amide, C.sub.1-C.sub.6alkoxy,
C.sub.1-C.sub.6thioalkyl, C.sub.1-C.sub.6perfluoroalkoxy,
--NH.sub.2, Cl, Br, I, F, --NH-lower alkyl, and --N(lower
alkyl).sub.2. However, any of the other suitable substituents known
to one skilled in the art can also be used in these
embodiments.
[0039] As used herein "mass addition polymerization" means
polymerizing one or more olefinic monomers neat without any
solvent. It also includes other terms used in the art such as
"bulk" polymerization or "in-mold" polymerization, and the like, in
each of such methods no solvent is employed. However, the
initiator/catalyst can be dissolved in some other solvent and/or in
the monomer itself to initiate such "mass addition polymerization"
methods as described herein.
[0040] As used herein "telechelic polymer" means a polymer having
one or more reactive end groups which is available for reacting
with another reactant.
[0041] It should be noted that any atom with unsatisfied valences
in the text, schemes, examples and tables herein is assumed to have
the appropriate number of hydrogen atom(s) to satisfy such
valences.
[0042] By the term, "a monomer repeat unit is derived" is meant
that the polymeric repeating units are polymerized (formed) from,
e.g., polycyclic norbornene-type monomers, wherein the resulting
polymers are formed by 2,3 enchainment of norbornene-type monomers
as shown below:
##STR00002##
[0043] Surprisingly, it has now been found that certain of the
bicycloalkenes of formula (I) as described herein facilitates
remarkably mass polymerization of a variety of polycycloolefin
monomers.
[0044] Accordingly, there is provided a reaction composition
comprising:
[0045] a compound of formula (I):
##STR00003##
[0046] wherein
[0047] a is an integer from 0 to 4;
[0048] b is an integer from 0 to 2a+4;
[0049] each R is hydrogen, halogen, methyl, ethyl, linear or
branched (C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy, linear or branched
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy;
[0050] one or more polycyclic olefin monomers; and
[0051] an organo-transition metal compound.
[0052] The compounds of formula (I) generally function as an
effective chain transfer agent during mass polymerization of one or
more monomers as described herein. Accordingly, any of the
compounds of formula (I) can be used in this invention which brings
about the effects of chain transfer property. Surprisingly, it has
now been found that any of the bicycloalkenes which have a ring
strain such that it acts effectively as a chain transfer agent can
be used. However, it should be noted that various other known mono-
or polycycloolefinic compounds having a ring strain energy greater
than 17 kcal/mole are also suitable as chain transfer agents for
mass polymerization of certain polycyclic olefin monomers of
formula (II) as described hereinbelow. Examples of such olefins
include trans-cyclooctene, norbornene, cyclobutene and the like.
More specifically, compounds of formula (I) are found to be
effective as chain transfer agents for the polymerization of
certain polycyclic olefin monomers of formula (II).
[0053] The compounds of formula (I) can be synthesized by any of
the procedures known to one skilled in the art. Specifically, some
of the compounds of formula (I) are known in the literature and
others can be prepared by methods used to prepare similar compounds
as reported in the literature and as further described herein.
[0054] More specifically, the compounds of formula (I) as disclosed
herein can be synthesized according to the following procedures of
Scheme 1, wherein a, b and R are as defined for Formula I unless
otherwise indicated.
##STR00004##
[0055] In general, in Scheme I, the compound of formula (IA) is
subjected to suitable reaction conditions to form a compound of
formula (I) in the presence of a suitable solvent. Such reaction
conditions that may be suitable for such conversions include
photolytic or thermolytic reaction conditions. It has been reported
in the literature that compounds of formula (IA) can conveniently
be converted to compounds of formula (I) by subjecting it to
suitable photolysis in the presence of a hydrocarbon solvent such
as heptane. See, for example, Liu, Robert S. H., Journal of
American Chemical Society (1967), 89(1), 112-114. However, any
other reaction condition that is known to one skill in the art to
make the compounds of formula (I) can also be employed.
[0056] One or more non-limiting examples of compound of formula
(I), where a=0, is selected from the group consisting of: [0057]
bicyclo[2.2.0]hex-2-ene; [0058] 5-methylbicyclo[2.2.0]hex-2-ene;
and [0059] 5,6-dimethylbicyclo[2.2.0]hex-2-ene.
[0060] One or more non-limiting examples of compound of formula
(I), where a=1 to 4, is selected from the group consisting of:
[0061] bicyclo[3.2.0]hept-6-ene; [0062]
2-methylbicyclo[3.2.0]hept-6-ene; [0063]
2,4-dimethylbicyclo[3.2.0]hept-6-ene; [0064]
2,4,6-trimethylbicyclo[3.2.0]hept-6-ene; [0065]
bicyclo[4.2.0]oct-7-ene; [0066] 2-methylbicyclo[4.2.0]oct-7-ene;
[0067] 3-methylbicyclo[4.2.0]oct-7-ene; [0068]
2,3-dimethylbicyclo[4.2.0]oct-7-ene; [0069]
2,3,5-trimethylbicyclo[4.2.0]oct-7-ene; [0070]
2,3,4,5-tetramethylbicyclo[4.2.0]oct-7-ene; [0071]
bicyclo[5.2.0]non-8-ene; [0072] 2-methylbicyclo[5.2.0]non-8-ene;
[0073] 2,5-dimethylbicyclo[5.2.0]non-8-ene; [0074]
bicyclo[6.2.0]dec-9-ene; and [0075]
2-methylbicyclo[6.2.0]dec-9-ene.
[0076] In another embodiment the reaction composition of this
invention encompasses a compound of formula (I) selected from the
group consisting of: [0077] bicyclo[3.2.0]hept-6-ene; [0078]
bicyclo[4.2.0]oct-7-ene; [0079] bicyclo[5.2.0]non-8-ene; and [0080]
bicyclo[6.2.0]dec-9-ene.
[0081] In yet another embodiment the composition of this invention
encompasses a compound of formula (I) selected from the group
consisting of: [0082] bicyclo[4.2.0]oct-7-ene; [0083]
2-methylbicyclo[4.2.0]oct-7-ene; [0084]
3-methylbicyclo[4.2.0]oct-7-ene; [0085]
2,3-dimethylbicyclo[4.2.0]oct-7-ene; [0086]
2,3,5-trimethylbicyclo[4.2.0]oct-7-ene; and [0087]
2,3,4,5-tetramethylbicyclo[4.2.0]oct-7-ene.
[0088] In a further aspect of this invention, any of the polycyclic
olefin monomers can be used in this aspect of the invention. For
instance, the reaction composition of this invention can encompass
one or more polycyclic olefin monomer of the formula (II):
##STR00005##
[0089] wherein:
[0090] c is an integer 0, 1 or 2;
[0091] R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or
different and each independently of one another is selected from
hydrogen, linear or branched (C.sub.1-C.sub.16)alkyl,
hydroxy(C.sub.1-C.sub.16)alkyl, perfluoro(C.sub.1-C.sub.12)alkyl,
(C.sub.3-C.sub.12)cycloalkyl, (C.sub.6-C.sub.12)bicycloalkyl,
(C.sub.7-C.sub.14)tricycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.3)alkyl,
perfluoro(C.sub.6-C.sub.10)aryl,
perfluoro(C.sub.6-C.sub.10)aryl(C.sub.1-C.sub.3)alkyl,
di(C.sub.1-C.sub.2)alkylmaleimide(C.sub.3-C.sub.6)alkyl,
di(C.sub.1-C.sub.2)alkylmaleimide(C.sub.2-C.sub.6)alkoxy(C.sub.1-C.sub.2)-
alkyl, hydroxy, (C.sub.1-C.sub.12)alkoxy,
(C.sub.3-C.sub.12)cycloalkoxy, (C.sub.6-C.sub.12)bicycloalkoxy,
(C.sub.7-C.sub.14)tricycloalkoxy,
(C.sub.6-C.sub.10)aryloxy(C.sub.1-C.sub.3)alkyl,
(C.sub.5-C.sub.10)heteroaryloxy(C.sub.1-C.sub.3)alkyl,
(C.sub.6-C.sub.10)aryloxy, (C.sub.5-C.sub.10)heteroaryloxy,
(C.sub.1-C.sub.6)acyloxy, where each of the aforementioned
substituents are optionally substituted with a group selected from
halogen or hydroxy.
[0092] Representative examples of monomers of formula (II) include
the following without any limitations:
##STR00006## ##STR00007## ##STR00008##
[0093] Accordingly, in one of the embodiments the reaction
composition of this invention encompasses one or more monomer of
formula (II) selected from the group consisting of: [0094]
bicyclo[2.2.1]hept-2-ene (NB); [0095]
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
[0096] 5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB); [0097]
5-octylbicyclo[2.2.1]hept-2-ene (OctNB); [0098]
5-decylbicyclo[2.2.1]hept-2-ene (DecNB); [0099]
5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C.sub.4F.sub.9NB); [0100]
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and [0101]
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).
[0102] In a further embodiment of this invention the composition of
this invention encompasses one or more monomers of formula (II) are
at least two distinct types of monomers of formula (II).
[0103] In yet another embodiment the composition of this invention
encompasses at least one of the monomers of formula (II), which is
5-decylbicyclo[2.2.1]hept-2-ene (DecNB).
[0104] In yet another embodiment the composition of this invention
encompasses at least one of the monomers of formula (II), which is
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB).
[0105] In yet another embodiment the composition of this invention
encompasses at least one of the monomers of formula (II), which is
5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB).
[0106] In a further aspect of this invention any amount of compound
of formula (I) can be employed in the reaction composition of this
invention which brings about the intended effect. That is, any
amount of compound of formula (I) can be employed such that one or
more monomers of formula (II) can be polymerized under mass
polymerization conditions employing a suitable transition metal
compound. Accordingly, in one of the embodiments, the composition
of this invention encompasses a compound of formula (I) in an
amount of at least one (1) mole percent of the total loading of the
monomers of formula (II). That is, a compound of formula (I) is
present at least at a one (1) mole percent level compared to the
total amount of one or more monomers of formula (II). In yet
another embodiment the composition of this invention encompasses
compound of formula (I) in an amount of from one (1) to ten (10)
mole percent of the total loading of the monomers of formula (II).
In yet another embodiment the composition of this invention
encompasses compound of formula (I) in an amount of from five (5)
to fifty (50) mole percent of the total loading of the monomers of
formula (II). In further embodiments the compound of formula (I)
can present at a level higher than 5 mol %; higher than 10 mol %;
higher than 20 mol %; higher than 30 mol %; or higher than 40 mol
%.
[0107] In another embodiment of this invention the reaction
composition of this invention includes an organo-transition metal
compound which facilitates the polymerization of the polycyclic
olefin in the presence of a chain transfer agent under mass
polymerization conditions. Generally, such organometallic compounds
are capable of reacting with the chain transfer agent to form an
intermediate "transition metal-hydride," which reacts further with
the olefinic monomer thus initiating the polymerization. Various
organo-transition metal compounds that brings about such a reaction
can be used in this invention. In some embodiments of this
invention such organo-transition metal compounds include compounds
formed from nickel, palladium or platinum, among others. Other
suitable transition metals include any of the Group X transition
metal or Group IX metal, such as for example, cobalt, rhodium or
iridium.
[0108] In another embodiment of this invention the
organo-transition metal compound includes a Lewis Base, which is
coordinately bonded to the metal atom, M. That is, the Lewis Base
is bonded to the metal atom by sharing both of its lone pair of
electrons. Any of the Lewis Base known in the art can be used for
this purpose. Advantageously, it has now been found that a Lewis
Base, which can dissociate readily under the polymerization
conditions as described further in detail below generally provides
more suitable compounds of formula (I) as polymerization catalysts.
Thus, in one aspect of this invention judicious selection of the
Lewis Base will provide a modulation of the catalytic activity of
the compounds of this invention.
[0109] Accordingly, it has now been found that suitable LBs that
can be employed include without any limitation substituted and
unsubstituted nitriles, including alkyl nitrile, aryl nitrile or
aralkyl nitrile; phosphine oxides, including substituted and
unsubstituted trialkyl phosphine oxides, triaryl phosphine oxides,
triaralkyl phosphine oxides, and various combinations of alkyl,
aryl and aralkyl phosphine oxides; substituted and unsubstituted
pyrazines; substituted and unsubstituted pyridines; phosphites,
including substituted and unsubstituted trialkyl phosphites,
triaryl phosphites, triaralkyl phosphites, and various combinations
of alkyl, aryl and aralkyl phosphites; phosphines, including
substituted and unsubstituted trialkyl phosphines, triaryl
phosphines, triaralkyl phosphines, and various combinations of
alkyl, aryl and aralkyl phosphines. Various other LBs that may be
employed include various ethers, alcohols, ketones, amines and
anilines, arsines, stibines, and the like.
[0110] In an embodiment of this invention, the LB is selected from
acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile,
benzonitrile (C.sub.6H.sub.5CN), 2,4,6-trimethylbenzonitrile,
phenyl acetonitrile (C.sub.6H.sub.5CH.sub.2CN), pyridine,
2-methylpyridine, 3-methylpyridine, 4-methylpyridine,
2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine,
2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine,
2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine, 2-methoxypyridine,
3-methoxypyridine, 4-methoxypyridine, pyrazine,
2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether,
dibenzyl ether, tetrahydrofuran, tetrahydropyran, benzophenone,
triphenylphosphine oxide, triphenyl phosphate and PR.sub.3, where R
is independently selected from methyl, ethyl,
(C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy,
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy. Representative examples of PR.sub.3
include without any limitation trimethyl phosphine, triethyl
phosphine, tri-n-propyl phosphine, tri-iso-propyl phosphine,
tri-n-butyl phosphine, tri-iso-butyl phosphine, tri-tert-butyl
phosphine, tricyclopentylphosphine, triallylphosphine,
tricyclohexylphosphine, triphenyl phosphine, trimethyl phosphite,
triethyl phosphite, tri-n-propyl phosphite, tri-iso-propyl
phosphite, tri-n-butyl phosphite, tri-iso-butyl phosphite,
tri-tert-butyl phosphite, tricyclopentylphosphite,
triallylphosphite, tricyclohexylphosphite, triphenyl phosphite, and
the like. It should however be noted that various other known LBs
which will bring about the intended activity can also be used in
this embodiment of the invention.
[0111] Other examples of organophosphorus compounds suitable as LBs
include phosphinite and phosphonate ligands. Representative
examples of phosphinite ligands include but are not limited to
methyl diphenylphosphinite, ethyl diphenylphosphinite, isopropyl
diphenylphosphinite, and phenyl diphenylphosphinite. Representative
examples of phosphonite ligands include but are not limited to
diphenyl phenylphosphonite, dimethyl phenylphosphonite, diethyl
methylphosphonite, diisopropyl phenylphosphonite, and diethyl
phenylphosphonite.
[0112] In a further aspect of this invention, it has now been found
that the organo-transition metal compound having a counter anion,
Z.sup..crclbar., which is a weakly coordinating anion (WCA)
provides better catalytic activity. That is, the WCA is an anion
which is only weakly coordinated to the cation complex. It is
sufficiently labile to be displaced by a neutral Lewis base,
solvent or monomer. More specifically, the WCA anion functions as a
stabilizing anion to the cation complex and does not form a
covalent bond with the metal atom, M. The WCA anion is relatively
inert in that it is non-oxidative, non-reducing, and
non-nucleophilic.
[0113] In general, the WCA can be selected from borates,
phosphates, arsenates, antimonates, aluminates, boratobenzene
anions, carborane, halocarborane anions, sulfonamidate and
sulfonates.
[0114] Broadly speaking, suitable borate anion can be represented
by Formula A, phosphate, arsenate and antimonate anions can be
represented by Formula B, and aluminate anions can be represented
by Formula C:
[M.sub.a(R.sub.a)(R.sub.b)(R.sub.c)(R.sub.d)]A
[M.sub.b(R.sub.a)R.sub.b)(R.sub.c)(R.sub.d)(R.sub.e)(R.sub.f)]B
[M.sub.c(OR.sub.a)(OR.sub.b)(OR.sub.c)(OR.sub.d)]C
[0115] Wherein in Formula A, M.sub.a is boron, in Formula B M.sub.b
is phosphorus, arsenic or antimony, in Formula C, M.sub.c is
aluminum. R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f
independently represent fluorine, linear and branched
C.sub.1-C.sub.10 alkyl, linear and branched C.sub.1-C.sub.10
alkoxy, linear and branched C.sub.3-C.sub.5 haloalkenyl, linear and
branched C.sub.3-C.sub.12 trialkylsiloxy, C.sub.18-C.sub.36
triarylsiloxy, substituted and unsubstituted C.sub.6-C.sub.30 aryl,
and substituted and unsubstituted C.sub.6-C.sub.30 aryloxy groups
wherein R.sub.a to R.sub.f cannot all simultaneously represent
alkoxy or aryloxy groups. When substituted the aryl groups can be
monosubstituted or multisubstituted, wherein the substituents are
independently selected from linear and branched C.sub.1-C.sub.5
alkyl, linear and branched C.sub.1-C.sub.5 haloalkyl, linear and
branched C.sub.1-C.sub.5 alkoxy, linear and branched
C.sub.1-C.sub.5 haloalkoxy, linear and branched C.sub.1-C.sub.12
trialkylsilyl, C.sub.6-C.sub.18 triarylsilyl, and halogen selected
from chlorine, bromine, and fluorine.
[0116] Representative borate anions of Formula A include but are
not limited to tetrafluoroborate, tetraphenylborate,
tetrakis(pentafluorophenyl)borate,
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,
tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,
tetrakis(2,3,4,5-tetrafluorophenyl)borate,
tetrakis(3,4,5,6-tetrafluorophenyl)borate,
tetrakis(3,4,5-trifluorophenyl)borate,
methyltris(perfluorophenyl)borate,
ethyltris(perfluorophenyl)borate,
phenyltris(perfluorophenyl)borate,
tetrakis(1,2,2-trifluoroethylenyl)borate,
tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,
tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,
(triphenylsiloxy)tris(pentafluorophenyl)borate,
(octyloxy)tris(pentafluorophenyl)borate,
tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]pheny-
l]borate,
tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]--
5-(trifluoromethyl)phenyl]borate, and
tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-
ethyl]-5-(trifluoromethyl)phenyl]borate.
[0117] Representative phosphates, arsenates, antimonates of Formula
B include but are not limited to hexafluorophosphate,
hexaphenylphosphate, hexakis(pentafluorophenyl)phosphate,
hexakis(3,5-bis(trifluoromethyl)phenyl)phosphate,
hexafluoroarsenate, hexaphenylarsenate,
hexakis(pentafluorophenyl)arsenate,
hexakis(3,5-bis(trifluoromethyl)phenyparsenate,
hexafluoroantimonate, hexaphenylantimonate,
hexakis(pentafluorophenyl)antimonate,
hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate, and the
like.
[0118] Representative aluminate anions of Formula C include but are
not limited to tetrakis(pentafluorophenyl)aluminate,
tris(nonafluorobiphenyl)fluoroaluminate,
(octyloxy)tris(pentafluorophenyl)aluminate,
tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, and
methyltris(pentafluorophenyl)aluminate.
[0119] In an embodiment of this invention suitable Z.sup..crclbar.
is selected from B(C.sub.6F.sub.5).sub.4.sup..crclbar.,
B[C.sub.6H.sub.3(CF.sub.3).sub.2].sub.4.sup..crclbar.,
B(C.sub.6H.sub.5).sub.4.sup..crclbar.,
[Al(OC(CF.sub.3).sub.2C.sub.6F.sub.5).sub.4].sup..crclbar.,
BF.sub.4.sup..crclbar., PF.sub.6.sup..crclbar.,
AsF.sub.6.sup..crclbar., SbF.sub.6.sup..crclbar.,
(CF.sub.3SO.sub.2)N.sup..crclbar. and
CF.sub.3SO.sub.3.sup..crclbar..
[0120] In one of the embodiments of this invention, the reaction
composition of this invention encompasses an organo-transition
metal compound of the formula (III):
##STR00009##
wherein,
[0121] LB is selected from pyridine, acetonitrile or
C.sub.6H.sub.5CN;
[0122] Z.sup..crclbar. is selected from
B(C.sub.6F.sub.5).sub.4.sup..crclbar.,
B(C.sub.6H.sub.5).sub.4.sup..crclbar., BF.sub.4.sup..crclbar. or
CF.sub.3SO.sub.3.sup..crclbar.;
[0123] R.sub.6 is independently selected from methyl, ethyl,
(C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy,
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy; and
[0124] R.sub.5 is methyl, ethyl, linear or branched
(C.sub.3-C.sub.6)alkyl, (C.sub.6-C.sub.10)aralkyl or R.sub.7CO,
where R.sub.7 is methyl, ethyl or (C.sub.3-C.sub.6)alkyl.
[0125] In a further embodiment of this invention the compound of
formula (III) is having the following substituents:
[0126] LB is acetonitrile;
[0127] Z.sup..crclbar. is
B(C.sub.6F.sub.5).sub.4.sup..crclbar.;
[0128] R.sub.6 is n-propyl, isopropyl, tert-butyl or phenyl;
and
[0129] R.sub.5 is n-propyl, isopropyl, tert-butyl or
--OCOCH.sub.3.
[0130] In another embodiment the reaction composition of this
invention encompasses an organo-transition metal compound
represented by formula (IIIA):
##STR00010##
wherein:
[0131] LB is acetonitrile or pyridine;
[0132] Z.sup..crclbar. is selected from
B(C.sub.6F.sub.5).sub.4.sup..crclbar. or BF.sub.4.sup..crclbar.;
and
[0133] R.sub.5 is isopropyl or --OCOCH.sub.3.
[0134] In this aspect of the embodiment, the compound of formula
(IIIA) is having the substituents as follows:
[0135] LB is either acetonitrile or pyridine; Z.sup..crclbar. is
B(C.sub.6F.sub.5).sub.4.sup..crclbar. or
BF.sub.4.sup..crclbar..
[0136] In yet another embodiment the reaction composition of this
invention encompasses an organo-transition metal compound
represented by formula (IIIB):
##STR00011##
[0137] In yet another embodiment the reaction composition of this
invention encompasses an organo-transition metal compound
represented by formula (IIIC):
##STR00012##
wherein Py is pyridine.
[0138] In yet another embodiment the reaction composition of this
invention encompasses an organo-transition metal compound
represented by formula (IIID):
##STR00013##
wherein Py is pyridine.
[0139] In another embodiment the reaction composition of this
invention encompasses an organo-transition metal compound
represented by formula (IV):
##STR00014##
wherein:
[0140] X is chlorine or triflate; and
[0141] R.sub.5 is n-propyl, isopropyl or --OCOCH.sub.3.
[0142] In further embodiments of this invention the compound of
formula (IV) encompasses where R.sub.5 is isopropyl or n-propyl; or
where R.sub.5 is --OCOCH.sub.3.
[0143] Non-limiting exemplary compounds of formula (IV), can be
represented by formulae (IVA), (IVB) or (IVC):
##STR00015##
[0144] In another embodiment of this invention, non-limiting
examples of one or more organo-transition metal compounds that can
be employed in the reaction composition can be selected from the
group consisting of: [0145]
trans-[Pd(NCMe)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub.6F.sub.5).sub.4,
[0146]
trans-[Pd(NCC(CH.sub.3).sub.3)(OAc)(P(i-propyl).sub.3).sub.2]B(C.s-
ub.6F.sub.5).sub.4, [0147]
trans-[Pd(OC(C.sub.6H.sub.5).sub.2)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub-
.6F.sub.5).sub.4, [0148]
trans-[Pd(HOCH(CH.sub.3).sub.2)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub.6F.-
sub.5).sub.4, [0149]
trans-[Pd(NCMe)(OAc)(P(cyclohexyl).sub.3).sub.2]B(C.sub.6F.sub.5).sub.4,
[0150] Pd(OAc).sub.2(P(cyclohexyl).sub.3).sub.2, [0151]
Pd(OAc).sub.2(P(i-propyl).sub.3).sub.2, [0152]
Pd(OAc).sub.2(P(i-propyl).sub.2(phenyl)).sub.2, [0153]
trans-[Pd(NCMe)(OAc)(P(cyclohexyl).sub.2(t-butyl)).sub.2]B(C.sub.6F.sub.5-
).sub.4, where OAc is OCOCH.sub.3.
[0154] In yet another embodiment of this invention, further
non-limiting examples of one or more organo-transition metal
compounds that can be employed in the reaction composition can be
selected from the group consisting of: [0155]
nickel(2,4,6-trifluoromethylphenyl).sub.2; [0156]
nickel(.eta..sup.6-toluene)(pentafluorophenyl).sub.2; [0157] nickel
(tetrahydrofuran).sub.2(pentafluorophenyl).sub.2; [0158]
[(allyl)Ni(1,4-cyclooctadiene)]PF.sub.6, [0159]
[(crotyl)Ni(1,4-cyclooctadiene)]PF.sub.6; and [0160]
[(allyl)Ni(1,4-cyclooctadiene)]SbF.sub.6.
[0161] In another aspect of this invention, the reaction
composition of this invention encompassing the organo-transition
metal compound, such as for example, a compound of formula (III) or
a compound of formula (IV) can be further admixed in-situ with
certain of the compounds of formula (V), as discussed below, to
form very active bicomponent initiator systems. It has now
surprisingly been found that such catalyst systems are very useful
for preparing a variety of polymers from certain of the cyclo
olefinic monomers as described herein under mass polymerization
conditions and avoid extraneous ligands, such as acetonitrile.
[0162] Accordingly, the reaction composition of this invention
further encompasses a compound of the formula (V):
M.sub.d.sup..sym.Z.sup..crclbar. (V);
[0163] wherein
[0164] M.sub.d.sup..sym. is a cation selected from lithium, sodium,
potassium, cesium, barium, ammonium and linear or branched
tetra(C.sub.1-C.sub.4)alkyl ammonium;
[0165] Z.sup..crclbar. is a weakly coordinating anion selected from
selected from B(C.sub.6F.sub.5).sub.4.sup..crclbar.,
B[C.sub.6H.sub.3(CF.sub.3).sub.2].sub.4.sup..crclbar.,
B(C.sub.6H.sub.5).sub.4.sup..crclbar.,
[Al(OC(CF.sub.3).sub.2C.sub.6F.sub.5).sub.4].sup..crclbar.,
BF.sub.4.sup..crclbar., PF.sub.6.sup..crclbar.,
AsF.sub.6.sup..crclbar., SbF.sub.6.sup..crclbar.,
(CF.sub.3SO.sub.2)N.sup..crclbar. and
CF.sub.3SO.sub.3.sup..crclbar.
[0166] Further, the compound of formula (V) is selected from the
group consisting of: [0167] lithium tetrafluoroborate; [0168]
lithium triflate; [0169] lithium tetrakis(pentafluorophenyl)borate;
[0170] lithium (diethyl ether) tetrakis(pentafluorophenyl)borate
([Li(OEt.sub.2).sub.2.5][B(C.sub.6F.sub.5).sub.4]) (LiFABA); [0171]
lithium tetraphenylborate; [0172] lithium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; [0173] lithium
tetrakis(2-fluorophenyl)borate; [0174] lithium
tetrakis(3-fluorophenyl)borate; [0175] lithium
tetrakis(4-fluorophenyl)borate; [0176] lithium
tetrakis(3,5-difluorophenyl)borate; [0177] lithium
hexafluorophosphate; [0178] lithium hexaphenylphosphate; [0179]
lithium hexakis(pentafluorophenyl)phosphate; [0180] lithium
hexafluoroarsenate; [0181] lithium hexaphenylarsenate; [0182]
lithium hexakis(pentafluorophenyl)arsenate; [0183] lithium
hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; [0184] lithium
hexafluoroantimonate; [0185] lithium hexaphenylantimonate; [0186]
lithium hexakis(pentafluorophenyl)antimonate; [0187] lithium
hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; [0188] lithium
tetrakis(pentafluorophenyl)aluminate; [0189] lithium
tris(nonafluorobiphenyl)fluoroaluminate; [0190] lithium
(octyloxy)tris(pentafluorophenyl)aluminate; [0191] lithium
tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; and [0192]
lithium methyltris(pentafluorophenyl)aluminate.
[0193] As noted, the polymerization reactions can be carried out
neat, i.e., under mass polymerization conditions. That is, by
practice of the instant invention it is now possible to make a
variety of polymers containing at least one functionalized
norbornene monomer (i.e., a compound of formula (II)) in the
presence of a chain transfer agent, i.e. a compound of formula (I).
The polymerizations are generally carried out in the presence of an
organo-transition metal compound, such as for example, an
unicomponent initiator (i.e., a compound of formula (III)) or a
bicomponent initiator (i.e., a compound of formula (IV) as
initiator) in combination with a compound of formula (V) as
activator) as described herein. However, it should be noted that
even when an unicomponent initiator, such as, compound of formula
(III) or other similar palladium compound as described herein is
employed, it has now been found that it may be advantageous to use
a compound of formula (V) as an activator compound in combination
with any of the unicomponent initiator compound as described
herein.
[0194] It has also been found that the organo-transition metal
compounds as described herein either as unicomponent or bicomponent
compositions as described herein are highly active. Thus it is now
possible to make polymers of high quality by employing small
amounts of these compounds as polymerization initiators.
Accordingly, in one of the embodiments the addition polymerization
can effectively be carried out using monomer to unicomponent
initiator molar ratio of at least 100:1 based on the total moles of
monomers and the initiator employed. That is, 100 moles of monomer
to one mole of the unicomponent initiator is employed. In other
embodiments the molar ratio of monomer:catalyst can be 1,000,000:1;
500,000:1; 100,000:1; 20,000:1; 10,000:1, 5,000:1, 500:1, 400:1,
200:1, and the like. When bicomponent initiator systems are
employed the molar ratio of monomer:initiator:activator can be at
least 100:1:1. In other embodiments the molar ratio of
monomer:initiator:activator can be 1,000,000:1:1; 500,000:1:1;
100,000:1:1; 20,000:1:1; 10,000:1:1, 1,000:1:1, 500:1:1, 400:1:1,
200:1:1, and the like. In some embodiments the activator is used in
excess of the mole quantities of the initiator used, such as for
example, molar ratios of initiator:activator can be from 1:1 to
1:6.
[0195] As noted, the mass polymerization reaction can be carried
out with catalyst and monomer without any solvent. Advantageously,
such polymerization reactions can also be carried out in a mold at
a suitable temperature to form three dimensional polymeric
products. In general, the reaction temperatures can range from
sub-ambient temperature, such as for example below 0.degree. C. to
boiling point of the monomers, however, it is recommended that the
components of the reaction vessel or the mold is not heated beyond
the flash points of one or more of the monomers. Generally, the
mass polymerization is carried out at a temperature range from
about 10.degree. C. to 300.degree. C., in some other embodiments
the temperature range can be from about 10.degree. C. to
200.degree. C.; or from about 20.degree. C. to 100.degree. C.
[0196] Since the polymerization reaction is exothermic, the
temperature in the mold during the course of the polymerization is
usually higher than the temperature of the feed, unless a chilled
mold is employed. Accordingly, the initial mold temperature can
generally be within the range of about -20.degree. C. to about
300.degree. C.; or from about 0.degree. C. to about 200.degree. C.;
or from 20.degree. C. and 100.degree. C. Temperature distribution
in the mold is affected by such factors as mold geometry,
characteristics of the mold as a heat sink or heat supplying means,
reactivity of catalyst and monomer, and the like. To some extent,
the selection of suitable temperatures and heat exchange conditions
will have to be based on experience with a given system of mold,
feed and catalyst.
[0197] After the polymerization reaction is complete, the molded
object may be subjected to an additional post cure treatment at a
temperature in the range of about 100.degree. C. to 300.degree. C.
for about 15 minutes to 24 hours; or 1 to 2 hours. Such a post cure
treatment can enhance polymeric properties including glass
transition temperature (T.sub.g) and heat distortion temperature
(HDT). In addition, postcuring is desirable but not essential, to
bring the samples to their final stable dimensional states, to
minimize residual odors, and to improve final physical
properties.
[0198] Advantageously, it has now been found that the mass
polymerization of the reaction compositions of this invention can
conveniently be carried out by heating the composition in stages:
first heating the reaction composition to a temperature of from
about 80.degree. C. to 110.degree. C. and maintaining at that
temperature for some time, for example from about 5 minutes to 1
hour; and then heating the composition to a second temperature of
from about 110.degree. C. to 140.degree. C. and maintaining at that
temperature for some time, for example from about 5 minutes to 1
hour.
[0199] In some other embodiments it has also been found that
carrying out the mass polymerization in more than two gradient
temperature offers better polymerized product. Accordingly, in one
of the embodiments the polymerization is carried out by heating the
reaction composition of this invention in four incremental
temperature ranges as follows: first heating the reaction
composition to a temperature of from about 40.degree. C. to
60.degree. C. and maintaining at that temperature for about 5
minutes to 1 hour; then heating the composition to a second
temperature of from about 60.degree. C. to 80.degree. C. and
maintaining at that temperature for about 5 minutes to 1 hour; then
heating the composition to a third temperature of from about
80.degree. C. to 100.degree. C. and maintaining at that temperature
for about 5 minutes to 1 hour; and finally heating the composition
to a fourth temperature of from about 100.degree. C. to 120.degree.
C. and maintaining at that temperature for about 5 minutes to 1
hour. However, it should be noted that any of the other temperature
and time conditions can also be employed to form polymers from the
reaction compositions of this invention and of such conditions are
within the scope of this invention.
[0200] The polymers formed according to this invention generally
exhibit a weight average molecular weight (M.sub.w) of at least
about 3,000. In another embodiment, the polymer of this invention
has a M.sub.w of at least about 5,000. In another embodiment, the
polymer of this invention has a M.sub.w of at least about 10,000.
In another embodiment, the polymer of this invention has a M.sub.w
of at least about 20,000. In yet another embodiment, the polymer of
this invention has a M.sub.w of at least about 50,000. In some
other embodiments, the polymer of this invention has a M.sub.w of
at least about 100,000. In another embodiment, the polymer of this
invention has a M.sub.w of higher than 100,000 and can be higher
than 500,000 in some other embodiments. The weight average
molecular weight (M.sub.w) of the polymers can be determined by any
of the known techniques, such as for example, by gel permeation
chromatography (GPC) equipped with suitable detector and
calibration standards, such as differential refractive index
detector calibrated with narrow-distribution polystyrene standards.
The polydispersity index (PDI), which is a ratio of weight average
molecular weight (M.sub.w) to number average molecular weight
(M.sub.n) can also be measured from this method.
[0201] In another aspect of this invention there is also provided a
method of mass polymerizing polycyclic olefin monomers
comprising:
[0202] combining a compound of formula (I):
##STR00016##
[0203] wherein
[0204] a is an integer from 0 to 4;
[0205] b is an integer from 0 to 2a+4;
[0206] each R is hydrogen, halogen, methyl, ethyl,
(C.sub.3-C.sub.6)alkyl, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkyl, (C.sub.6-C.sub.10)aryl,
(C.sub.6-C.sub.10)aralkyl, methoxy, ethoxy,
(C.sub.3-C.sub.6)alkoxy, substituted or unsubstituted
(C.sub.3-C.sub.7)cycloalkoxy, (C.sub.6-C.sub.10)aryloxy and
(C.sub.6-C.sub.10)aralkyloxy;
[0207] with one or more polycyclic olefin monomers; and an
organo-transition metal compound to form a mixture; and
[0208] polymerizing the mixture to form a polymer.
[0209] As noted, one or more compounds of formula (I) as described
herein can be combined with one or more of a polycyclic olefin
monomers, such as the ones described herein having the formula (II)
in the presence of one or more of an organo-transition compounds as
described herein to form the polymers under mass polymerization
conditions as described herein. Any of the known reaction
conditions can be employed to form such polymers, including the
temperature and "in mold" conditions described hereinabove.
[0210] In an embodiment of this invention the method of this
invention includes a compound of formula (I), which activates said
organo-transition metal compound by forming a metal-hydride
containing moiety. In this aspect of the invention the
organo-transition metal compound is a palladium compound.
[0211] In a further embodiment of this invention the method of this
invention further comprises adding one or more compounds of the
formula (V). Any of the compounds of formula (V) as described
hereinabove can be employed in this aspect of the method of this
invention.
[0212] In addition, any of the organo-transition compounds as
described herein including the compounds of formulae (III), (IIIA),
(IIIB), (IIIC), (IIID), as well as any of the compounds of formulae
(IV), (IVA), (IVB) and (IVC) can be used in the method of this
invention.
[0213] Advantageously, it has now been found that various other
palladium compounds can also be employed in the method of this
invention. Such palladium compounds suitable for forming polymers
using the reaction composition of this invention are represented by
the formula:
(Allyl)Pd(P(Q.sub.3).sub.3)(L.sub.1) or
(methyl)Pd(P(Q.sub.3).sub.3)(L.sub.1)
wherein Q may be the same or different and is independently
selected from isopropyl, tert-butyl, neopentyl and cyclohexyl; and
L.sub.1 is selected from halogen, trifluoroacetate, and
trifluoromethanesulfonate (triflate). Non-limiting examples of such
palladium compounds include the following: [0214]
allylpalladium(triisopropylphosphine) chloride,
[Pd(allyl)(triisopropylphosphine)Cl]; [0215]
allylpalladium(tri-tert-butylphosphine) chloride,
[Pd(allyl)(tri-tert-butylphosphine)Cl]; [0216]
allylpalladium(diisopropyl-tert-butylphosphine) chloride,
[Pd(allyl)(diisopropyl-tert-butylphosphine)Cl]; [0217]
(allyl)palladium(tricyclohexylphosphine)triflate,
[Pd(allyl)(tricyclohexylphosphine)triflate]; [0218]
(allyl)palladium(triisopropylphosphine)triflate,
[Pd(allyl)(triisopropylphosphine)triflate]; [0219]
(allyl)palladium(tricyclohexyl phosphine)trifluoroacetate,
[Pd(allyl)(tricyclohexylphosphine)trifluoroacetate]; [0220]
(allyl)palladium(triisopropylphosphine)trifluoroacetate,
[Pd(allyl)(triisopropylphosphine)trifluoroacetate]; [0221]
methylpalladium(triisopropylphosphine) chloride,
[Pd(methyl)(triisopropylphosphine)Cl]; [0222]
methylpalladium(tri-tert-butylphosphine) chloride,
[Pd(methyl)(tri-tert-butylphosphine)Cl]; [0223]
methylpalladium(diisopropyl-tert-butylphosphine) chloride,
[Pd(methyl)(diisopropyl-tert-butylphosphine)Cl]; [0224]
methylpalladium(tricyclohexylphosphine) chloride,
[Pd(methyl)(tricyclohexylphosphine)Cl], also abbreviated as
[(Me-Pd-PCy.sub.3)Cl], where Cy is cyclohexyl (C.sub.6H.sub.11);
[0225] methylpalladium(dicyclohexyl-tert-butylphosphine) chloride,
[Pd(methyl)(dicyclohexyl-tert-butylphosphine)Cl]; [0226]
methylpalladium(cyclohexyl-di(tert-butyl)phosphine) chloride,
[Pd(methyl)(cyclohexyl-di(tert-butyl)phosphine)Cl]; and the
like.
[0227] As also noted above, the palladium compounds as mentioned
above are generally used in conjunction with an additional compound
which functions as a cocatalyst, initiator, pro-initiator or
activator. For example, any of the compounds of formula (V) as
described hereinabove can be used for this purpose. In one of the
embodiments, non-limiting examples of such activator compounds
include lithium tetrakis(pentafluorophenyl)borate etherate
(LiFABA-[Li(OEt.sub.2).sub.2.5][B(C.sub.6F.sub.5).sub.4]) and
N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate (DANFABA),
and the like.
[0228] Thus it should be noted that the palladium containing
catalysts useful for making the polymers from the reaction
composition of this invention can be prepared as a preformed single
component catalyst or prepared in situ by admixing a palladium
containing procatalyst with an activator (or a cocatalyst,
initiator or pro-initiator, as mentioned above) in the presence of
the desired monomer(s) to be polymerized.
[0229] Accordingly, the preformed initiator can be prepared by
admixing the initiator precursors such as a procatalyst and
activator (or a cocatalyst, initiator or pro-initiator) in an
appropriate solvent, allowing the reaction to proceed under
appropriate temperature conditions, and isolating the reaction
product, that is, a preformed initiator product. By procatalyst is
meant a palladium containing compound that is converted to an
active initiator by a reaction with a cocatalyst, activator or
pro-initiator compound. Further description and synthesis of
representative procatalysts and activator compounds can be found in
U.S. Pat. No. 6,455,650, pertinent portions of which are
incorporated herein by reference.
[0230] In one of the embodiments, various polymers can be formed by
practicing the method of this invention. Non-limiting examples of
such polymers formed from the method of this invention may be
enumerated as follows:
[0231] a polymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene
(HexNB);
[0232] a polymer derived from 5-decylbicyclo[2.2.1]hept-2-ene
(DecNB); and
[0233] a polymer derived from 5-phenethylbicyclo[2.2.1]hept-2-ene
(PENB).
[0234] The following examples are detailed descriptions of methods
of preparation and use of certain compounds/monomers, polymers and
compositions of the present invention. The detailed preparations
fall within the scope of, and serve to exemplify, the more
generally described methods of preparation set forth above. The
examples are presented for illustrative purposes only, and are not
intended as a restriction on the scope of the invention. As used in
the examples and throughout the specification the ratio of monomer
to catalyst is based on a mole to mole basis.
[0235] This invention is further illustrated by the following
examples which are provided for illustration purposes and in no way
limit the scope of the present invention.
EXAMPLES
[0236] The following abbreviations have been used hereinbefore and
hereafter in describing some of the compounds, instruments and/or
methods employed to illustrate certain of the embodiments of this
invention:
DecNB: 5-decylbicyclo[2.2.1]hept-2-ene; HexNB:
5-hexylbicyclo-[2.2.1]hept-2-ene; PENB:
5-phenethylbicyclo[2.2.1]hept-2-ene; BCO--bicyclo[4.2.0]oct-7-ene;
DANFABA--N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate;
LiFABA--lithium tetrakis(pentafluoro-phenyl)borate;
TBS--tri-n-butylsilane; THF--tetrahydrofuran; CTA--chain transfer
agent; GPC: gel permeation chromatography; M.sub.w--weight average
molecular weight; PD--polydispersity; .sup.1H NMR--proton nuclear
magnetic resonance spectroscopy.
[0237] The following examples describe the procedures used for the
preparation of various polymers as disclosed herein. However, it
should be noted that these examples are intended to illustrate the
disclosure without limiting the scope thereof.
[0238] The following Examples 1 to 11 illustrate the mass
polymerization of DecNB using two different palladium
compounds.
Examples 1-5
[0239] The following Examples 1-5 demonstrate the effects of
various levels of BCO on homopolymer molecular weight.
[0240] Into a suitable reactor purged with nitrogen were placed
5000 parts of DecNB, one part of palladium compound
(AcO--Pd--NCCH.sub.3(P-i-Pr.sub.3).sub.2B(C.sub.6F.sub.5).sub.4)
and 2 parts of DANFABA. To this mixture was then added desirable
amounts of BCO ranging from 1 mole percent to 7.5 mole percent
based on the amount of monomer employed, as summarized in Table 1.
The reaction mixture was then heated to 85.degree. C. and
maintained at this temperature for 30 minutes and then heated to
110.degree. C. and maintained at that temperature for 30 minutes.
After which time the reaction mixture was allowed to cool to room
temperature. The resulting products in each of the Examples 1 to 5
were characterized by GPC in THF, the M.sub.w and PD for each of
the Examples 1 to 5 are summarized in Table 1. The thermal
stability of each of the polymer products from Examples 1 to 5 were
also analyzed by TGA, the temperature at which 5 weight percent
loss of the polymer products are also summarized in Table 1. In
addition, the percent weight loss of the monomer during
polymerization was also measured and is summarized in Table 1 for
each of the Examples 1 to 5.
TABLE-US-00001 TABLE 1 Example Mol % % Weight GPC TGA, .degree.C.
No. BCO Loss M.sub.w/PD (5% weight loss) 1 1 4 125,000/4.5 354 2 2
5.3 76,000/4.5 359 3 3.3 5.2 54,000/4.4 352 4 5 5.8 28,000/3.3 356
5 7.5 5.6 25,000/3.3 344 Comp. Ex. 1 0 5 Insoluble 357
[0241] Also summarized in Table 1 is the data obtained from
Comparative Example 1 which contained no BCO. It is quite evident
from this data that BCO has surprising effect on controlling the
molecular weight of poly(DecNB), and one can control the molecular
weight of the resulting polymer simply by the amount of BCO
employed.
[0242] The polymer obtained from Example 5 (5 mol % BCO) was also
characterized by 1H NMR, which confirmed that the BCO is inserted
into the end of the polymer chain having structure as shown
below.
##STR00017##
Examples 6-11
[0243] The procedures of Examples 1 to 5 were substantially
repeated in these Examples 6 to 11 except that
(iso-propoxy-dicyclopentadienyl)chloropalladium(triisopropyl)phosphine
[Pd(i-PrO-DCPD)Cl(P-i-Pr.sub.3)] was used as the palladium
initiator in combination with LiFABA in the ratio of 5000 parts of
DecNB as the monomer, 1 part of palladium compound and 1 part of
LiFABA. In addition, the mole percent of BCO employed were varied
as summarized in Table 2. Also summarized Table 2 are the percent
weight loss of the monomer, the M.sub.w and PD as determined by GPC
of each of the polymer products obtained and the 5% weight loss of
the polymer product as determined by the TGA.
TABLE-US-00002 TABLE 2 Example Mol % % Weight GPC TGA, .degree.C.
No. BCO Loss M.sub.w/PD (5% weight loss) 6 1 4.5 54,000/3.5 369 7
3.3 4.8 36,000/3.5 368 8 4 5 29,000/3.4 365 9 5 5.1 22,000/3 354 10
7.5 6.9 15,000/2.7 346 11 10 6.6 13,000/2.8 345 Comp. Ex. 2 0 7
Insoluble 363
[0244] It is again evident that BCO acts as an effective chain
transfer agent in Examples 6-11. Furthermore, these Examples
illustrate that depending upon the type of metal initiator employed
it is now possible to obtain a polycycloolefin polymer having
desirable properties based on the amount of BCO used as evidenced
by the above examples.
Examples 12-14
Mass Polymerization of HexNB
[0245] Into a suitable reactor purged with nitrogen were placed
10,000 parts of HexNB, 1 part of palladium compound,
trans-[Pd(NCMe)(OAc)(P(i-propyl).sub.3).sub.2]B(C.sub.6F.sub.5).sub.4,
also referred to herein as
(AcO--Pd--NCCH.sub.3(P-i-Pr.sub.3).sub.2B(C.sub.6F.sub.5).sub.4),
and 2 parts of DANFABA. To this mixture was then added desirable
amounts of BCO as follows: 5 mole percent in Example 12, 7.5 mole
percent in Example 13 and 10 mole percent in Example 14. Each of
the reaction mixture was heated in stages at four different
temperatures: first heated to 50.degree. C. and maintained at this
temperature for 30 minutes, heated to 65.degree. C. and maintained
at that temperature for 30 minutes, then heated to 85.degree. C.
and maintained at that temperature for 30 minutes and finally
heated to 110.degree. C. and maintained at that temperature for 30
minutes. After which time the reaction mixture was allowed to cool
to room temperature. The resulting products in each of the Examples
12 to 14 were characterized by GPC in THF, the M.sub.w and PD for
each of the Examples 12 to 14 are as follows: Example
12--M.sub.w/PD 53,700/4.2; Example 13--M.sub.w/PD 30,800/4.8; and
Example 14--M.sub.w/PD 22,000/4.4.
Examples 15-17
Mass Polymerization of PENB
[0246] Into a suitable reactor purged with nitrogen were placed
10,000 parts of PENB, 1 part of palladium compound
(AcO--Pd--NCCH.sub.3(P-i-Pr.sub.3).sub.2B(C.sub.6F.sub.5).sub.4)
and 2 parts of DANFABA. To this mixture was then added desirable
amounts of BCO as follows: 5 mole percent in Example 15, 7.5 mole
percent in Example 16 and 10 mole percent in Example 17. Each of
the reaction mixture was heated in stages at four different
temperatures: first heated to 50.degree. C. and maintained at this
temperature for 30 minutes, heated to 65.degree. C. and maintained
at that temperature for 30 minutes, then heated to 85.degree. C.
and maintained at that temperature for 30 minutes and finally
heated to 110.degree. C. and maintained at that temperature for 30
minutes. After which time the reaction mixture was allowed to cool
to room temperature. The resulting products in each of the Examples
15 to 17 were characterized by GPC in THF, the M.sub.w and PD for
each of the Examples 15 to 17 are as follows: Example
15--M.sub.w/PD 34,900/5.7; Example 16--M.sub.w/PD 20,800/4.6; and
Example 17--M.sub.w/PD 16,800/4.7.
Example 18
Thermogravimetric Analysis
[0247] The polymer products from Examples 1 to 5 were also tested
for their thermal stability by thermogravimetric analysis (TGA).
FIG. 1 shows the thermograms obtained for each of the samples
respectively from Examples 1 to 5. It is evident from this data
that onset of thermal decomposition depends upon the amount of BCO
used to form the polymer. The insoluble polymer formed without any
BCO exhibited an onset of decomposition temperature (T.sub.d) of
374.degree. C. Addition of BCO as chain transfer agent gradually
decreased the Td from 364.degree. C. with 5 mole % BCO to
324.degree. C. with 50 mole % BCO.
[0248] For comparative purposes, similar TGA analyses were also
conducted for polymer products obtained from Comparative Example 3
where various amounts of tri-n-butyl silane (TBS) was used as the
chain transfer agent. The results are shown in FIG. 2. It is
evident from FIG. 2 that use of TBS as a chain transfer agent
results in markedly less thermally stable polymers in that the best
onset of decomposition temperature (T.sub.d) was observed to be
288.degree. C. with 5 mol % TBS, and the Td significantly decreases
to 178.degree. C. with 20 mol % TBS. Whereas the polymers obtained
in accordance with this invention exhibit T.sub.d ranging from
324.degree. C. to 364.degree. C. as shown in FIG. 1 and as
discussed above. This clearly demonstrates the superior properties
that can be obtained from the practice of this invention.
Comparative Example 1
[0249] The procedures of Examples 1 to 5 were substantially
repeated in this Comparative Example 1 except that no BCO was used
in this Comparative Example 1. The polymer product obtained in this
Comparative Example 1 was insoluble in THF.
Comparative Example 2
[0250] The procedures of Examples 6 to 11 were substantially
repeated in this Comparative Example 2 except that no BCO was used
in this Comparative Example 2. The polymer product obtained in this
Comparative Example 2 was insoluble in THF.
Comparative Examples 3-7
Mass Polymerization Using TBS as a CTA
[0251] The procedures of Examples 1 to 5 were substantially
repeated in this Comparative Example 3 except that various amounts
of TBS was used as a chain transfer agent instead of BCO, and
1-decanol was used as an activating agent, the amounts of TBS and
1-decanol used in each of these Comparative Examples 3 to 7 are
summarized in Table 3 as mole % of the DecNB monomer used to make
the polymer.
TABLE-US-00003 TABLE 3 Comparative Mol % % Weight GPC TGA,
.degree.C. Example No. TBS/1-decanol Loss M.sub.w/PD (5% weight
loss) 3 0/0 7.8 Insoluble 365 4 5/5 10.3 42,900/4.3 288 5 7.5/7/5
12.1 27,200/3.4 237 6 10/10 13.4 20,300/3 210 7 20/20 17.9
8,100/2.2 178
[0252] Also summarized in Table 3 are the percent weight loss of
the monomer during polymerization, the M.sub.w and PD as measured
by GPC using THF as the solvent and the T.sub.d (5% weight loss) as
determined by TGA. It is evident from the data presented in Table
3, a combination of TBS and 1-decanol results in significantly
increased monomer loss during polymerization as evidenced by very
high amount of monomer loss shown as % weight loss of the monomer,
an indication of poor conversion. The M.sub.w of the resulting
polymer was also significantly lower than that of the polymers
obtained in accordance with this invention. More importantly the
thermal stability of the polymers obtained in these Comparative
Examples 3 to 7 are much inferior to the polymers obtained in
accordance with this invention. This is further discussed and
illustrated in Example 18 and shown in FIGS. 1 and 2.
Comparative Example 8
Cis-Cyclooctene as CTA
[0253] The procedures of Examples 1 to 5 were substantially
repeated in this Comparative Example 8 except that 20 mole % of
cis-cyclooctene was used as a chain transfer agent in this
Comparative Example 8. The polymer product obtained in this
Comparative Example 8 appears to form clear solution in THF, which
was filtered through 5 .mu.m filter. However, attempts to determine
the molecular weight of the polymer was not successful probably due
to the formation of microgels.
Comparative Examples 9 and 10
1-Hexene as CTA
[0254] The procedures of Examples 12 to 14 were substantially
repeated in these Comparative Examples 9 and 10 except for slight
modification in heating temperatures as described herein and for
using 1-hexene as a chain transfer agent (respectively 20 mol % and
5 mole % in Comparative Examples 9 and 10). Each of the reaction
mixture was heated in stages at three different temperatures: first
heated to 65.degree. C. and maintained at that temperature for 60
minutes, then heated to 85.degree. C. and maintained at that
temperature for 30 minutes and finally heated to 130.degree. C. and
maintained at that temperature for 30 minutes. After which time the
reaction mixture was allowed to cool to room temperature. The
resulting products in each of the Comparative Examples 9 and 10
were insoluble in THF, thus evidencing that 1-hexene does not
function as an effective chain transfer agent under these
conditions.
Comparative Examples 11 to 13
Formic Acid as CTA
[0255] The procedures of Examples 1 to 5 were substantially
repeated in these Comparative Examples 11 to 13 except that
respectively 20 mole %, 10 mol % and 5 mol % of formic acid was
used as a chain transfer agent in these Comparative Examples 11 to
13. In each of these Comparative Examples 11 to 13, the reaction
product mostly solidified and only a portion of the solid sample
was soluble in THF in Comparative Examples 11 and 12, and the
polymer product in Comparative Example 13 dissolved in THF but the
solution was hazy. The GPC results of the soluble portion of the
polymeric samples revealed that very high M.sub.w were achieved
with very high PDs under these polymerization conditions as
follows: Comparative Example 11, M.sub.w 1,180,000, PD 9;
Comparative Example 12, M.sub.w 2,02,000, PD 10; and Comparative
Example 13, M.sub.w 850,000, PD 14. This clearly demonstrates that
formic acid is not effective as a chain transfer agent under these
conditions.
[0256] Although the invention has been illustrated by certain of
the preceding examples, it is not to be construed as being limited
thereby; but rather, the invention encompasses the generic area as
hereinbefore disclosed. Various modifications and embodiments can
be made without departing from the spirit and scope thereof.
* * * * *